CN110684524A - Electroluminescent compound, thermal activation delayed fluorescence material and application thereof - Google Patents
Electroluminescent compound, thermal activation delayed fluorescence material and application thereof Download PDFInfo
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- CN110684524A CN110684524A CN201911063213.8A CN201911063213A CN110684524A CN 110684524 A CN110684524 A CN 110684524A CN 201911063213 A CN201911063213 A CN 201911063213A CN 110684524 A CN110684524 A CN 110684524A
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- electroluminescent compound
- integer
- delayed fluorescence
- layer
- fluorescence material
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- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic System
- C07F5/02—Boron compounds
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- H10K50/12—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers comprising dopants
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Abstract
The invention provides an electroluminescent compound, a thermal activation delayed fluorescence material and application thereof. The electroluminescent compound has TADF (thermo-activated delayed fluorescence) characteristics, can be used as a thermal activation delayed fluorescence material to be applied to a light emitting layer of an OLED (organic light emitting diode) device, the OLED device comprises an anode, a cathode and at least one organic thin film layer positioned between the anode and the cathode, and the thermal activation delayed fluorescence material is contained in the light emitting layer in the organic thin film layer. The electroluminescent compound provided by the invention effectively reduces the overlapping between HOMO and LUMO through the special design of the molecular structure, so that Delta E is obtainedSTDown to 0.25eVThe reverse crossing of the triplet state energy to the singlet state is met, the transmission capability of two carriers is effectively improved, the carrier balance is improved, and the light emitting efficiency of the OLED device is remarkably improved.
Description
Technical Field
The invention belongs to the technical field of organic electroluminescent materials, and particularly relates to an electroluminescent compound, a thermal activation delayed fluorescence material and application thereof.
Background
An Organic Light Emitting Display (OLED) is a novel flat panel Display technology, and compared with a Liquid Crystal Display (LCD), an OLED has the advantages of active Light emission, high response speed, low energy consumption, low driving voltage, lightness, thinness, wide viewing angle, continuously adjustable Light Emitting color, low cost, simple production process, high Light Emitting efficiency, flexible Display and the like, and has gained great attention in the industry and the scientific community, and is widely applied to industries such as flexible Display, flat panel Display, solid state lighting, vehicle-mounted Display and the like. At present, OLEDs have entered the industrial stage, and the development of high-performance organic photoelectric materials remains a focus of the field.
Studies have shown that light-emitting layer materials for OLEDs can be classified into the following four types according to their light-emitting mechanisms: fluorescent materials, phosphorescent materials, triplet-triplet annihilation (TTA) materials, and Thermally Activated Delayed Fluorescence (TADF) materials. Wherein the singlet excited state S of the fluorescent material1Transition back to ground state S by radiation0According to the spin statistics, the ratio of singlet excitons to triplet excitons in the excitons is 1:3, so that the maximum internal quantum yield of the fluorescent material is not more than 25%; according to the lambertian emission mode, the light extraction efficiency is about 20%, so the external quantum efficiency EQE of the phosphor-based OLED device is generally not higher than 5%. Triplet excited state T of phosphorescent material1Attenuation of direct radiation to the ground state S0Due to the heavy atom effect, the intramolecular intersystem crossing can be enhanced through the spin coupling effect, 75% of triplet excitons can be directly utilized, and the S-shaped quantum dots can be realized at room temperature1And T1The maximum theoretical internal quantum yield can reach 100 percent by jointly participating in emission; according to the lambertian light emitting mode, the light extraction efficiency is about 20%, so the EQE of the OLED device based on the phosphorescent material can reach 20%; however, most phosphorescent materials are heavy metal complexes such as Ir, Pt, Os, Re, Ru and the like, and the production cost is high, so that the large-scale production is not facilitated; and under high current density, the phosphorescence material has a serious efficiency roll-off phenomenon, which causes poor stability of the phosphorescence light-emitting OLED device. Two triplet excitons of the TTA material interact with each other to generate a singlet excited state molecule with a higher energy level and a ground state molecule in a compounding manner; however, two triplet excitons generate one singlet exciton, so that the theoretical maximum internal quantum yield can only reach 62.5%; in order to prevent the generation of a large efficiency roll-off phenomenon, triplet excitons are generated in the processThe concentration of (c) needs to be regulated.
In TADF materials, when S is1State and T1Small difference in energy level of states, and T1Long service life of the state exciton, T under a certain temperature condition1The excitons in the state can reverse intersystem crossing (RISC), achieving T1State transition to S1The process of the state, again from S1Attenuation of state radiation to the ground state S0. Therefore, the TADF material can simultaneously utilize 75% of triplet excitons and 25% of singlet excitons, and the theoretical maximum internal quantum yield can reach 100%; more importantly, the TADF material is mainly an organic compound, does not need rare metal elements, has low production cost, and can be chemically modified by various methods to realize further optimization of performance.
CN109134520A, CN109503508A, CN108530357A, etc. disclose TADF materials and their applications, but currently, few TADF materials have been found, and the performance of the TADF materials is difficult to meet the requirements of people for high-performance OLED devices.
Therefore, the development of a wider variety of new TADF materials with high performance is a problem to be solved in the art.
Disclosure of Invention
In order to develop a wider variety of TADF materials with higher performance, it is an object of the present invention to provide an electroluminescent compound having a structure represented by formula I:
in the formula I, R, R1、R2、R3Each independently selected from any one of substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, and substituted or unsubstituted C6-C30 arylamino, and R, R1、R2、R3Are electron donating groups.
The C6 to C40 may be C7, C8, C10, C13, C15, C18, C20, C23, C25, C28, C30, C33, C35, C37, C39, or the like.
The C3 to C40 may be C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C28, C30, C33, C35, C37, C39, or the like.
The C6-C30 may be C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27 or C29.
The "electron donating group" means a group capable of increasing the electron cloud density on the benzene ring, and exemplarily includes but is not limited to carbazolyl, arylamine, acridine, phenothiazinyl, phenoxazinyl, or the like.
When the substituent exists in the groups, the substituent is selected from at least one of C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C1-C10 thioalkoxy.
The C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.
In the formula I, L is C6-C30 arylene or C3-C30 heteroarylene.
The C6-C30 may be C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27 or C29.
The C3 to C30 may be C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, C29, or the like.
In the formula I, n1Is an integer of 0 to 3, such as 0, 1, 2 or 3.
In the formula I, n2Is an integer of 0 to 4, such as 0, 1, 2, 3 or 4.
In the formula I, n3Is an integer of 0 to 2, such as 0, 1 or 2.
It is another object of the present invention to provide a thermally activated delayed fluorescence material, which includes any one or at least two combinations of the above electroluminescent compounds.
It is a further object of the present invention to provide a display panel comprising an OLED device comprising an anode, a cathode and at least 1 organic thin film layer between the anode and the cathode, the organic thin film layer comprising a light emitting layer.
The light emitting layer includes the thermally activated delayed fluorescence material as described above, and the thermally activated delayed fluorescence material is used as any one of a host material, a guest material, or a co-dopant material.
It is a fourth object of the present invention to provide an electronic device including the display panel as described above.
Compared with the prior art, the invention has the following beneficial effects:
(1) the electroluminescent compound provided by the invention is a boron heterocyclic ring-containing micromolecular compound, the aggregation of the compound is avoided through the access of a large steric hindrance group, and the direct accumulation of a conjugate plane to form pi aggregation or excimer is avoided, so that the luminous efficiency is improved.
(2) The thermal activation delayed fluorescence material based on the electroluminescent compound has TADF (TADF-activated fluorescent powder) characteristics, the structure with large rigidity distortion in molecules effectively reduces the overlapping between HOMO (highest energy density) and LUMO (Low energy density), so that the energy level difference between a triplet state and a singlet state can be reduced to be below 0.25eV (eV), even to be below 0.10eV, the reverse crossing of triplet state energy to the singlet state is met, the efficiency of a device is improved, the fluorescence life is greatly prolonged and reaches the level of mu s, and the obvious delayed fluorescence effect is achieved.
(3) The difference value between HOMO and LUMO of the electroluminescent compound provided by the invention is larger, the distortion degree of the compound is larger, the full-spectrum emission in visible light is realized through a substituent, and the electroluminescent compound can be used as a luminescent layer material of red light, blue light, green light and the like to be applied to various required luminescent layer materials.
(4) The parent structure (boron substituted naphthoquinoline) of the electroluminescent compound is dry, has good thermal stability, is not easy to decompose, has higher glass state transition temperature which can reach more than 100 ℃, and has amorphous state in the film forming process, so that the compactness of a film layer is better, and the stability of a device is higher. In addition, the parent structure of the electroluminescent compound has relatively small molecular weight, low evaporation temperature and low decomposition degree of the material, and can be applied to an evaporation process to obtain a high-performance OLED device.
(5) The electroluminescent compound provided by the invention has bipolar characteristics, can effectively improve the transmission capability of two carriers and improve the carrier balance as a light emitting layer of an OLED device, improves the luminous efficiency of the device, reduces the voltage of the device, enables the external quantum efficiency of the device to reach 16.5-23.5%, enables the current efficiency to reach 19.0-61.3 Cd/A, and can fully meet the application requirements of high-performance OLED devices.
Drawings
Fig. 1 is a schematic structural diagram of an OLED device provided in the present invention, in which 101 is an anode, 102 is a cathode, 103 is a light emitting layer, 104 is a first organic thin film layer, and 105 is a second organic thin film layer;
FIG. 2 is a HOMO orbital alignment of electroluminescent compound M1 provided in example 1 herein;
FIG. 3 shows the LUMO orbital layout of electroluminescent compound M1, provided in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
One of the objects of the present invention is to provide an electroluminescent compound having a structure represented by formula I:
in the formula I, R, R1、R2、R3Each independently selected from any one of substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, and substituted or unsubstituted C6-C30 arylamino, and R, R1、R2、R3Are electron donating groups.
The C6 to C40 may be C7, C8, C10, C13, C15, C18, C20, C23, C25, C28, C30, C33, C35, C37, C39, or the like.
The C3 to C40 may be C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C28, C30, C33, C35, C37, C39, or the like.
The C6-C30 may be C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27 or C29.
The "electron donating group" means a group capable of increasing the electron cloud density on the benzene ring, and exemplarily includes but is not limited to carbazolyl, arylamine, acridine, phenothiazinyl, phenoxazinyl, or the like.
When the substituent exists in the groups, the substituent is selected from at least one of C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C1-C10 thioalkoxy.
The C1-C10 can be C1, C2, C3, C4, C5, C6, C7, C8, C9 or C10.
In the formula I, L is C6-C30 arylene or C3-C30 heteroarylene.
The C6-C30 may be C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27 or C29.
The C3 to C30 may be C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, C29, or the like.
In the formula I, n1Is an integer of 0 to 3, such as 0, 1, 2 or 3.
In the formula I, n2Is an integer of 0 to 4, such as 0, 1, 2, 3 or 4.
In the formula I, n3Is an integer of 0 to 2, such as 0, 1 or 2.
The electroluminescent compound provided by the invention takes boron-substituted naphthoquinoline as a core and is used as an electron acceptor, a connecting group R and a connecting group R1、R2、R3As an electron donor, the aggregation of compounds is avoided through the access of large steric hindrance groups, and the direct accumulation of conjugated planes to form pi aggregation or excimer is avoided, so that the luminous efficiency is improved. The thermal activation delayed fluorescence material based on the electroluminescent compound has TADF (TADF characteristics), and can emit light by utilizing triplet excitons forbidden by the transition of the traditional fluorescent molecules, so that the efficiency of the device is improved; the fundamental reason is that the molecules of the electroluminescent compound have large rigid distortion, the overlapping between HOMO and LUMO is reduced, the energy level difference between a triplet state and a singlet state can be reduced to be less than 0.25eV, the reverse crossing of triplet state energy to the singlet state is met, and the device efficiency is improved; and realizes the full-spectrum emission in visible light through the special design of the substituent groupAnd (4) shooting. The electroluminescent compound has bipolar characteristics, and can effectively improve the transmission capability of two carriers and improve the carrier balance as a light emitting layer of an OLED device, improve the fluorescence quantum efficiency of the device and reduce the voltage of the device.
In one embodiment, said R, R1、R2、R3Each independently selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group.
Z1-Z7Each independently selected from O, S or N-RN1Any one of the above; the N-RN1Attached to the five-membered ring via the N atom. The same meanings are given below when referring to the same description.
U1、U2Each independently selected from O, S, N-RN2Or RC1-C-RC2Any one of the above; the N-RN2Linked to a six-membered ring through the N atom, said RC1-C-RC2Linked to the six-membered ring through the C atom. The same meanings are given below when referring to the same description.
RN1、RN2、RC1、RC2Any one selected from hydrogen, C1 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) straight-chain or branched-chain alkyl groups, C1 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) alkoxy groups, C6 to C20 (e.g., C7, C9, C10, C12, C14, C15, C17, or C19) aryl groups, C3 to C20 (e.g., C4, C6, C8, C10, C12, C14, C16, or C18) heteroaryl groups.
The substituent is at least one of C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) straight-chain or branched-chain alkyl, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) alkoxy or C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) thioalkoxy.
In one embodiment, the electroluminescent compound has a structure according to formula II:
in the formula II, R1、R2、R3Each independently having the same limitations as in formula I above.
In formula II, L is a C6-C30 (e.g., C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, or C29) arylene, or C3-C30 (e.g., C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, or C29) heteroarylene.
In the formula II, n1Is an integer of 0 to 3, such as 0, 1, 2 or 3.
In the formula II, n2Is an integer of 0 to 4, such as 0, 1, 2, 3 or 4.
In the formula II, n3Is an integer of 0 to 2, such as 0, 1 or 2.
In one embodiment, the electroluminescent compound has a structure according to formula III:
in the formula III, U is selected from O, S, N-RU1Or RU2-C-RU3Any one of the above; wherein R isU1、RU2、RU3Each independently selected from any one of hydrogen, C1 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) straight or branched alkyl groups, C1 to C10 (e.g., C2, C3, C4, C5, C6, C7, C8, or C9) alkoxy groups, C6 to C20 (e.g., C7, C9, C10, C12, C14, C15, C17, or C19) aryl groups, and C3 to C20 (e.g., C4, C6, C8, C10, C12, C14, C16, or C18) heteroaryl groups.
In the formula III, R1、R2、R3Each independently of the others as described aboveThe same limitations apply to formula I.
In formula III, L is a C6-C30 (e.g., C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, or C29) arylene, or C3-C30 (e.g., C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, or C29) heteroarylene.
In the formula III, n1 is an integer of 0-3, such as 0, 1, 2 or 3.
In the formula III, n2 is an integer of 0-4, such as 0, 1, 2, 3 or 4.
In the formula III, n3 is an integer of 0-2, such as 0, 1 or 2.
In one embodiment, the U is selected from O, S, N-RU1Or
Any one of (1), RU1And the aryl group is C6-C20 (for example, C7, C9, C10, C12, C14, C15, C17, C19 and the like) or C3-C20 (for example, C4, C6, C8, C10, C12, C14, C16, C18 and the like) heteroaryl.
In one embodiment, the electroluminescent compound has a structure according to formula IV:
in the formula IV, R1、R2、R3Each independently having the same limitations as in formula I above.
In formula IV, L is C6-C30 (e.g., C7, C8, C9, C10, C13, C15, C18, C20, C23, C25, C27, or C29) arylene, or C3-C30 (e.g., C4, C5, C6, C8, C10, C13, C15, C18, C20, C23, C25, C27, or C29) heteroarylene.
In the formula IV, n1Is an integer of 0 to 3, such as 0, 1, 2 or 3.
In the formula IV, n2Is an integer of 0 to 4, such as 0, 1, 2, 3 or 4.
In the formula IV, n3Is an integer of 0 to 2, such as 0, 1 or 2.
In one embodiment, L is selected from the group consisting of arylene of C6-C24 (e.g., C7, C8, C9, C10, C13, C15, C18, C20, C22, C23, etc.), heteroarylene of C3-C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.), heteroarylene containing N, or heteroarylene of C3-C20 (e.g., C4, C6, C8, C10, C12, C14, C16, C18, etc.) containing O.
In one embodiment, L is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
In one embodiment, said R is1、R2、R3Each independently selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group.
The substituent is at least one of C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) straight-chain or branched-chain alkyl, C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) alkoxy or C1-C10 (such as C2, C3, C4, C5, C6, C7, C8 or C9) thioalkoxy.
In one embodiment, the electroluminescent compound is selected from any one of the following compounds M1 to M50:
it is another object of the present invention to provide a thermally activated delayed fluorescence material, which includes any one or at least two combinations of the above electroluminescent compounds.
In one embodiment, the thermally activated delayed fluorescence material has the lowest singlet state S1With the lowest triplet state T1Energy difference between states Δ EST＝ES1-ET1Less than or equal to 0.30eV, e.g. energy level difference Δ EST0.29eV, 0.27eV, 0.25eV, 0.24eV, 0.23eV, 0.22eV, 0.21eV, 0.20eV, 0.19eV, 0.18eV, 0.16eV, 0.14eV, 0.13eV, 0.12eV, 0.11eV, 0.10eV, 0.09eV, 0.08eV, 0.07eV, 0.06eV, 0.05eV, 0.04eV, 0.03eV, 0.02eV, or 0.01 eV.
It is a further object of the present invention to provide a display panel comprising an OLED device comprising an anode, a cathode and at least 1 organic thin film layer between the anode and the cathode, the organic thin film layer comprising a light emitting layer.
The light emitting layer includes the thermally activated delayed fluorescence material as described above, and the thermally activated delayed fluorescence material is used as any one of a host material, a guest material, or a co-dopant material.
In one embodiment, the organic thin film layer further includes any one of a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron transport layer, an electron injection layer, or a combination of at least two thereof.
In the OLED device, the anode material can be metal, metal oxide or conductive polymer; wherein the metal includes copper, gold, silver, iron, chromium, nickel, manganese, palladium, platinum, etc., and alloys thereof, the metal oxide includes Indium Tin Oxide (ITO), Indium Zinc Oxide (IZO), zinc oxide, Indium Gallium Zinc Oxide (IGZO), etc., and the conductive polymer includes polyaniline, polypyrrole, poly (3-methylthiophene), etc. In addition to the above materials that facilitate hole injection and combinations thereof, known materials suitable for use as anodes are also included.
In the OLED device, the cathode material can be metal or a multi-layer metal material; wherein the metal comprises aluminum, magnesium, silver, indium, tin, titanium and the like and alloys thereof, and the multilayer metal material comprises LiF/Al and LiO2/Al、BaF2Al, etc. In addition to the above materials and combinations thereof that facilitate electron injection, known materials suitable for use as cathodes are also included.
In the OLED device, the organic thin film layer comprises at least one light-emitting layer (EML) and any one or combination of at least two of a Hole Transport Layer (HTL), a Hole Injection Layer (HIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL) and an Electron Injection Layer (EIL) which are arranged on two sides of the light-emitting layer, wherein the hole/electron injection and transport layer can be carbazole compounds, arylamine compounds, benzimidazole compounds, metal compounds and the like.
The OLED device is schematically illustrated in fig. 1, and includes an anode 101 and a cathode 102, a light emitting layer 103 disposed between the anode 101 and the cathode 102, and a first organic thin film layer 104 and a second organic thin film layer 105 disposed on two sides of the light emitting layer 103, where the first organic thin film layer 104 and the second organic thin film layer 105 are each independently any 1 or a combination of at least 2 of a Hole Transport Layer (HTL), a Hole Injection Layer (HIL), an Electron Blocking Layer (EBL), a Hole Blocking Layer (HBL), an Electron Transport Layer (ETL), and an Electron Injection Layer (EIL).
The OLED device can be prepared by the following method: an anode is formed on a transparent or opaque smooth substrate, an organic thin layer is formed on the anode, and a cathode is formed on the organic thin layer. Among them, known film forming methods such as evaporation, sputtering, spin coating, dipping, ion plating, and the like can be used to form the organic thin layer.
It is a fourth object of the present invention to provide an electronic device including the display panel as described above.
The compound provided by the invention and having the structure shown in the formula I is prepared by the following synthetic route:
wherein, R, R1、R2、R3、L、n1、n2、n3Each independently having the same limitations as in formula I above, TMS is trimethylsilyl.
Example 1
This example provides an electroluminescent compound having the following structure:
the preparation method comprises the following steps:
(1)
a (0.5mmol) and B (0.5mmol) were added sequentially to a microwave vial, dissolved in ethanol (6mL), and tetrabutylacetate (Bu) was added4NOAc, 1mmol) and Pd En Cat (63mg, 5 mol%); the reaction was irradiated with a microwave apparatus at 120 ℃ for 10 minutes. After cooling to room temperature in the microwave cavity, the reaction mixture was purified on a SCXII column using dichloromethane (DCM, 10mL) as eluent and evaporated to dryness to give intermediate C.
1H-NMR(400MHz，CDCl3)：δ8.91(s,1H),8.12(d,J＝4.0Hz,2H),7.84(s,1H),7.66(s,1H),7.53(s,1H),7.44(s,1H),7.32(d,J＝20.0Hz,2H)。
13C-NMR(100MHz，CDCl3)：δ148.63(s),148.12(s),147.36(s),143.88(s),134.18(s),132.82(s),131.31(s),130.07(s),129.65(s),127.95(s),127.51(s),126.95(s),120.99(s),119.91(s),118.80(s)。
(2)
A250 mL three-necked flask was charged with intermediate C7.22 g (20mmol), dissolved in tetrahydrofuran (THF, 80mL), and placed under nitrogenChanging for three times; cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-butyllithium 20mL (n-BuLi, 50mmol), stirring for 30 min; then 4.35g of trimethylchlorosilane (TMS-Cl, 40mmol) is slowly added dropwise, and the temperature is raised to 0 ℃ for reaction for 4 hours. Adding ice water for quenching after finishing; adding DCM for extraction, collecting an organic phase, and carrying out rotary evaporation to obtain a light yellow oily substance; crystallizing by using a mixed solvent of toluene and ethanol to obtain a light yellow solid; a pale yellow solid, 70mL of an anhydrous toluene solution and 0.76mL (8mmol) of boron tribromide were sequentially added to a 200mL closed tank, and the mixture was stirred at 120 ℃ for 12 hours. After the reaction is finished H2O (100mL) quench; extracting the reaction solution with DCM, collecting the organic phase, drying, filtering, and removing the solvent by rotary evaporation; and crystallizing by using a mixed solvent of dichloromethane and ethanol to obtain an intermediate D.
1H-NMR(400MHz，CDCl3)：δ8.87(s,1H),8.56(s,1H),8.17(s,1H),7.94(s,2H),7.77(s,1H),7.59(s,1H),7.50(s,1H),7.42(s,1H)。
13C-NMR(100MHz，CDCl3)：δ152.83(s),152.33(s),142.66(s),137.45(s),133.10(s),132.00(s),130.42(s),129.95(s),129.74(s),128.11(s),127.38(s),125.83(s),111.38(s)。
(3)
Adding 6.16g (19.13mmol) of compound E9- (4-bromophenyl) carbazole into a reaction bottle, dissolving with diethyl ether (50mL), and replacing with nitrogen for three times; cooling to-78 deg.C, controlling temperature below-65 deg.C, slowly adding n-BuLi8.04mL (2.5M, 20.09mmol), stirring for 30 min; 4.4g (15mmol) of intermediate D was dissolved in toluene (Tol, 60mL), and then slowly added dropwise to the reaction solution, after completion of the dropwise addition, the temperature was naturally raised to room temperature for reaction for 6 hours. After the reaction, ice water (100mL) was added to quench the reaction, DCM was added for extraction, and finally brine was added once for extraction. The organic phase was collected and rotary evaporated to give a pale yellow oil. Purifying the product by a column chromatography method (the mobile phase is a mixed solvent of n-hexane and dichloromethane in a volume ratio of 3: 1) to obtain a target product M1.
1H-NMR(400MHz，CDCl3)：δ8.87(s,1H),8.63(s,1H),8.55(s,1H),8.18(d,J＝8.0Hz,2H),7.94(s,2H),7.89(s,2H),7.75(d,J＝16.0Hz,3H),7.59(s,1H),7.51(d,J＝8.0Hz,2H),7.41(d,J＝8.0Hz,2H),7.16(dd,J＝22.0,14.0Hz,4H)。
13C-NMR(100MHz，CDCl3)：δ154.08(s),151.64(s),149.09(s),145.60(s),139.35(s),135.38(s),135.09(s),134.82(s),131.99(s),130.97(s),129.86–129.49(m),127.77(d,J＝9.8Hz),126.91(s),125.67(s),125.32(s),121.91(s),121.15(d,J＝2.7Hz),114.95(s),113.74(s)。
Example 2
This example provides an electroluminescent compound having the following structure:
the preparation method differs from the preparation method in example 1 in that the compound E in step (3) is used in an equimolar amount of the compound E2
Alternatively, other preparation conditions were unchanged to obtain the target product M2.
1H-NMR(400MHz，CDCl3)：δ8.87(s,1H),8.63(s,1H),8.55(s,1H),8.18(d,J＝8.0Hz,2H),7.94(s,4H),7.89(s,4H),7.75(d,J＝16.0Hz,3H),7.59(s,1H),7.51(d,J＝8.0Hz,2H),7.41(d,J＝8.0Hz,2H),7.16(dd,J＝22.0,14.0Hz,4H)。
13C-NMR(100MHz，CDCl3)：δ154.08(s),151.67(d,J＝7.0Hz),146.93(s),145.60(s),139.35(s),135.09(s),134.01(s),131.99(s),130.97(s),129.86-129.49(m),129.27(s),127.82(s),127.11(s),126.91(s),125.32(s),124.67(s),122.99(s),113.74(s)。
Example 3
This example provides an electroluminescent compound having the following structure:
the preparation method differs from the preparation method in example 1 in that the compound E in step (3) is used in an equimolar amount of the compound E3
Alternatively, other preparation conditions were unchanged to obtain the target product M3.
1H-NMR(400MHz，CDCl3)：δ8.87(s,1H),8.62(s,1H),8.17(s,1H),7.94(s,1H),7.74(d,J＝24.0Hz,3H),7.55(d,J＝36.0Hz,2H),7.42(s,1H),7.18(dd,J＝8.0,4.0Hz,8H),6.94(s,2H),1.69(s,6H)。
13C-NMR(100MHz，CDCl3)：δ154.08(s),152.78(s),151.64(s),145.60(s),142.44(s),139.35(s),135.09(s),134.24(s),133.37(s),131.99(s),130.97(s),29.86-129.49(m),128.95(s),127.82(s),127.11(s),126.83(d,J＝15.7Hz),125.32(s),122.86(s),120.00(s),113.74(s),35.71(s),29.68(s)。
Example 4
This example provides an electroluminescent compound having the following structure:
the preparation method differs from the preparation method in example 1 in that the compound E in step (3) is used in an equimolar amount of the compound E4
Alternatively, other preparation conditions were unchanged to obtain the target product M4.
1H-NMR(400MHz，CDCl3)：δ8.87(s,1H),8.64(s,1H),8.17(s,1H),7.94(s,1H),7.74(d,J＝24.0Hz,3H),7.55(d,J＝36.0Hz,2H),7.42(s,1H),7.27-7.00(m,6H),6.98(s,2H),6.93(s,2H)。
13C-NMR(100MHz，CDCl3)：δ154.08(s),152.78(s),151.64(s),146.79(s),145.60(s),139.35(s),135.09(s),134.24(s),132.27(s),131.99(s),130.97(s),129.86-129.49(m),127.82(s),127.11(s),126.91(s),125.32(s),123.59(d,J＝16.4Hz),119.00(s),116.41(s),113.74(s)。
Example 5
This example provides an electroluminescent compound having the following structure:
the preparation method differs from the preparation method in example 1 in that the compound E in step (3) is used in an equimolar amount of the compound E5Alternatively, other preparation conditions were unchanged to obtain the target product M5.
1H-NMR(400MHz，CDCl3)：δ8.87(s,1H),8.64(s,1H),8.17(s,1H),7.94(s,1H),7.74(d,J＝24.0Hz,3H),7.55(d,J＝36.0Hz,2H),7.42(s,1H),7.25-7.06(m,8H),6.97(s,2H).
13C-NMR(100MHz，CDCl3)：δ154.08(s),152.78(s),151.64(s),145.60(s),141.45(s),139.35(s),135.09(s),134.24(s),131.99(s),130.97(s),129.86-129.49(m),127.82(s),127.22-127.01(m),126.91(s),126.62(s),125.32(s),124.39(s),122.70(s),115.74(s),113.74(s).
Example 6
This example provides an electroluminescent compound having the following structure:
the preparation method differs from the preparation method in example 1 in that the compound E in step (3) is used in an equimolar amount of the compound E11
Alternatively, other preparation conditions were unchanged to obtain the target product M11.
1H-NMR(400MHz，CDCl3)：δ9.96(s,1H),8.87(s,1H),8.59(d,J＝30.8Hz,2H),8.18(d,J＝8.0Hz,2H),7.94(s,1H),7.77(s,3H),7.71-7.29(m,3H),7.41(d,J＝8.0Hz,2H),7.41(d,J＝8.0Hz,2H),7.16(dd,J＝22.0,14.0Hz,2H).
13C-NMR(100MHz，CDCl3)：δ154.08(s),151.64(s),146.81(s),145.60(s),139.95(s),137.03(s),135.23(s),134.62(s),134.27(s),132.22(s),131.39(s),129.98(s),129.61(d,J＝2.1Hz),127.35(d,J＝18.4Hz),126.10(s),125.05(s),122.16(s),120.90(s),116.82(s),113.74(s).
Application example 1
This application example provides an OLED device, OLED device includes in proper order: the structure comprises a substrate, an ITO anode, a hole injection layer, a hole transport layer, a light-emitting layer, a first electron transport layer, a second electron transport layer, a cathode (a magnesium-silver electrode, the mass ratio of magnesium to silver is 9:1) and a cap layer (CPL), wherein the thickness of the ITO anode is 15nm, the thickness of the hole injection layer is 10nm, the thickness of the hole transport layer is 110nm, the thickness of the light-emitting layer is 30nm, the thickness of the first electron transport layer is 30nm, the thickness of the second electron transport layer is 5nm, the thickness of the magnesium-silver electrode is 15nm, and the thickness of the cap layer (CPL) is 100 nm.
The preparation steps of the OLED device are as follows:
(1) cutting a glass substrate into sizes of 50mm multiplied by 0.7mm, respectively carrying out ultrasonic treatment in isopropanol and deionized water for 30 minutes, and then cleaning in ozone for 10 minutes; mounting the obtained glass substrate with the ITO anode on a vacuum deposition device;
(2) under vacuum degree of 2X 10-6Under Pa, performing vacuum evaporation on the ITO anode layer to form a hole injection layer material HAT-CN with the thickness of 10 nm;
(3) carrying out vacuum evaporation on the TAPC on the hole injection layer to form a hole transport layer with the thickness of 110 nm;
(4) co-depositing a light-emitting layer on the hole transport layer, wherein the electroluminescent compound M1 provided in example 1 of the present invention was used as a dopant material of the light-emitting layer, 3,3 '-bis (N-carbazolyl) -1,1' -biphenyl (mCBP) was used as a host material of the light-emitting layer, the mass ratio of M1 and mCBP was 1:9, and the thickness was 30 nm;
(5) vacuum evaporating TPBi on the luminous layer to be used as a first electron transport layer, wherein the thickness of the first electron transport layer is 30 nm;
(6) depositing Alq3 as a second electron transport layer on the first electron transport layer by vacuum evaporation, wherein the thickness is 5 nm;
(7) a magnesium silver electrode is evaporated on the second electron transport layer in vacuum to be used as a cathode, and the thickness is 15 nm;
(8) CBP was vacuum-evaporated on the cathode as a cathode cover layer (cap layer) to a thickness of 100 nm.
Application example 2
This application example differs from application example 1 in that M1 in step (4) is replaced with an equal amount of M2.
Application example 3
This application example differs from application example 1 in that M1 in step (4) is replaced with an equal amount of M3.
Application example 4
This application example differs from application example 1 in that M1 in step (4) is replaced with an equal amount of M4.
Application example 5
This application example differs from application example 1 in that M1 in step (4) is replaced with an equal amount of M5.
Application example 6
This application example differs from application example 1 in that M1 in step (4) is replaced with an equal amount of M11.
Comparative example 1
This comparative example differs from application example 1 in that M1 in step (4) was used with an equal amount of the comparative compound BczVBi
And (6) replacing.
Comparative example 2
This comparative example differs from application example 1 in that M1 in step (4) was used in equal amounts of comparative Compound 1
And (6) replacing.
Comparative example 3
The present comparative example is different from application example 1 in that,the same amount of comparative Compound 2 was used for M1 in step (4)
And (6) replacing.
And (3) performance testing:
(1) simulated calculation of compounds:
the difference in the energy levels of the singlet and triplet states of the electroluminescent compounds can be achieved by Guassian 09 software (Guassian Inc.), the difference in energy levels Δ ESTThe specific simulation method can be referred to documents J.chem.Theory company, 2013, DOI:10.1021/ct400415r, and the optimization and excitation of the molecular structure can be completed by TD-DFT method "B3 LYP" and base group "6-31 g (d); the electroluminescent compounds M1, M2, M3, M4, M5, M11 and BczVBi provided by the present invention were simulated according to the above-described method, and the results are shown in table 1.
(2) Orbital alignment simulation of compounds:
the orbital layout of the electroluminescent compound M1 provided by the present invention was simulated according to methods known in the art, for example, see Furche F, Ahlrichs R.Adiabaltic time-dependent sensitivity functional method for exposed state properties [ J]Journal of Chemical Physics,2002,117(16):7433, wherein the arrangement of HOMO orbitals of M1 is shown in FIG. 2 and the arrangement of LUMO orbitals of M1 is shown in FIG. 3, and comparing FIGS. 2 and 3, it can be seen that the HOMO and LUMO of M1 are arranged in different regions, respectively, achieving complete separation, contributing to a reduction of the interstitial energy difference △ ESTThereby improving the anti-backlash crossing capability.
TABLE 1
As can be seen from the data in Table 1, the electroluminescent compounds provided by the present invention are △ E through the specific design of the molecular structureSTThe energy level difference of a singlet state and a triplet state is small, and the crossing of a reverse gap is facilitated; the fluorescence lifetime is greatly improved, can reach the level of mus, even reaches 14.0 mus, and has obvious delayed fluorescence effect. Compared with that in comparative exampleBczVBi, and is preferably used as a light-emitting layer material of an OLED device.
(3) Performance evaluation of OLED devices:
testing the current of the OLED device under different voltages by using a Keithley 2365A digital nano-volt meter, and then dividing the current by the light-emitting area to obtain the current density of the OLED device under different voltages; testing the brightness and radiant energy flux density of the OLED device under different voltages by using a Konicaminolta CS-2000 spectroradiometer; according to the current density and the brightness of the OLED device under different voltages, the current density (10 mA/cm) is obtained under the same current density2) Current efficiency (Cd/A) and external quantum efficiency (%). The OLED devices provided in application examples 1-6 and comparative examples 1-3 were tested for their turn-on voltage (V) according to the method described aboveturn-on) Current Efficiency (CE), External Quantum Efficiency (EQE), power efficiency (hp) and chromaticity coordinates CIE (x, y), the results are shown in table 2.
TABLE 2
From the data in table 2, compared with the OLED device using the existing light-emitting layer doped material BczVBi in the comparative example 1, the OLED device prepared by using the electroluminescent compound provided in the embodiments 1 to 6 of the present invention as the light-emitting layer material has lower turn-on voltage, higher current efficiency, power efficiency and external quantum efficiency, the current efficiency of the OLED device reaches 19.0 to 61.3Cd/a, the power efficiency reaches 19.4 to 58.4lm/W, and the external quantum efficiency is higher than 16.59%, even reaches 23.4%STThe organic light emitting diode can be used as a light emitting layer material of an OLED device, the efficiency of the device can be effectively improved, and the turn-on voltage is reduced.
The electroluminescent compound provided by the invention can realize full-spectrum emission in visible light through the design of substituents, and according to data of chromaticity coordinates CIE (x, y) in Table 2, M1 and M5 can be used as blue light emitting layer materials of OLED devices, M2 can be used as green light emitting layer materials, M4 can be used as red light emitting layer materials, and M3 and M11 can be used as yellow light emitting layer materials.
The electroluminescent compound provided by the invention takes boron-substituted naphthoquinoline as a core and is used as an electron acceptor which is connected with R, R1、R2、R3Electron donor groups are provided with TADF characteristics, and triplet excitons which are forbidden by the transition of the traditional fluorescent molecules can be used for emitting light, so that the efficiency of the device is improved; in addition, the access of the large steric hindrance group avoids the aggregation of compounds, avoids the direct accumulation of conjugate planes to form pi aggregation or excimer, and is also favorable for improving the luminous efficiency of the device. If the core structures of the boron-substituted naphthoquinoline (the comparative compound 1 and the comparative compound 2) are not used, the OLED device which is used as the luminescent layer doping material has the advantages of increased lighting voltage and reduced luminous efficiency, and the performance requirements of a high-performance luminescent device are difficult to meet.
The applicant states that the present invention is illustrated by the above examples of the electroluminescent compounds, the thermally activated delayed fluorescence materials and their applications, but the present invention is not limited to the above process steps, i.e. it does not mean that the present invention must rely on the above process steps to be carried out. It will be apparent to those skilled in the art that any modification of the present invention, equivalent substitutions of selected materials and additions of auxiliary components, selection of specific modes and the like, which are within the scope and disclosure of the present invention, are contemplated by the present invention.
Claims (15)
1. An electroluminescent compound having a structure according to formula I:
wherein, R, R1、R2、R3Each independently selected from any one of substituted or unsubstituted C6-C40 aryl, substituted or unsubstituted C3-C40 heteroaryl, and substituted or unsubstituted C6-C30 arylamino, and R, R1、R2、R3Is an electron donating group;
when the substituent exists in the groups, the substituent is selected from at least one of C1-C10 straight-chain or branched-chain alkyl, C1-C10 alkoxy or C1-C10 thioalkoxy;
l is C6-C30 arylene or C3-C30 heteroarylene;
n1is an integer of 0 to 3;
n2is an integer of 0 to 4;
n3is an integer of 0 to 2.
2. An electroluminescent compound according to claim 1, wherein R, R is the compound1、R2、R3Each independently selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group;
Z1-Z7each independently selected from O, S or N-RN1Any one of the above;
U1、U2each independently selected from O, S, N-RN2Or RC1-C-RC2Any one of the above;
RN1、RN2、RC1、RC2any one of hydrogen, C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy, C6-C20 aryl and C3-C20 heteroaryl;
the substituent is at least one of C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy or C1-C10 thioalkoxy.
3. An electroluminescent compound according to claim 1, wherein the electroluminescent compound has a structure according to formula II:
wherein R is1、R2、R3Each independently having the same limitations as claim 1;
l is C6-C30 arylene or C3-C30 heteroarylene;
n1is an integer of 0 to 3;
n2is an integer of 0 to 4;
n3is an integer of 0 to 2.
4. An electroluminescent compound according to claim 1, wherein the electroluminescent compound has a structure according to formula III:
wherein U is selected from O, S, N-RU1Or RU2-C-RU3Any one of (1), RU1、RU2、RU3Each independently selected from any one of hydrogen, C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy, C6-C20 aryl and C3-C20 heteroaryl;
R1、R2、R3each independently having the same limitations as claim 1;
l is C6-C30 arylene or C3-C30 heteroarylene;
n1is an integer of 0 to 3;
n2is an integer of 0 to 4;
n3is an integer of 0 to 2.
5. An electroluminescent compound according to claim 4, wherein U is selected from O, S, N-RU1Or
Any one of (1), RU1Is C6-C20 aryl or C3-C20 heteroaryl.
6. An electroluminescent compound according to claim 1, wherein the electroluminescent compound has a structure according to formula IV:
wherein R is1、R2、R3Each independently having the same limitations as claim 1;
l is C6-C30 arylene or C3-C30 heteroarylene;
n1is an integer of 0 to 3;
n2is an integer of 0 to 4;
n3is an integer of 0 to 2.
7. An electroluminescent compound according to any one of claims 1 to 6, wherein L is selected from the group consisting of C6-C24 arylene, C3-C20N-containing heteroarylene, and C3-C20O-containing heteroarylene.
8. An electroluminescent compound according to claim 7, wherein L is selected from any one of the following groups:
wherein the dotted line represents the attachment site of the group.
9. Electroluminescent compound according to claim 1, characterized in that R is1、R2、R3Each independently selected from any one of the following groups, or any one of the following groups substituted by a substituent group:
wherein the dotted line represents the attachment site of the group;
the substituent is at least one of C1-C10 straight chain or branched chain alkyl, C1-C10 alkoxy or C1-C10 thioalkoxy.
10. An electroluminescent compound according to claim 1, wherein the electroluminescent compound is selected from any one of the following compounds M1 to M50:
11. a thermally activated delayed fluorescence material, wherein the thermally activated delayed fluorescence material comprises any one or at least two combinations of the electroluminescent compounds as claimed in any one of claims 1 to 10.
12. A thermally activated delayed fluorescence material as claimed in claim 11, wherein the lowest singlet state S of the thermally activated delayed fluorescence material1With the lowest triplet state T1Energy difference between states Δ EST＝ES1-ET1≤0.30eV。
13. A display panel comprising an OLED device comprising an anode, a cathode, and at least 1 organic thin film layer between the anode and the cathode, the organic thin film layer comprising a light emitting layer;
the light-emitting layer includes the thermally activated delayed fluorescence material according to claim 11 or 12, and the thermally activated delayed fluorescence material is used as any one of a host material, a guest material, or a co-dopant material.
14. The display panel according to claim 13, wherein the organic thin film layer further comprises any one of a hole transport layer, a hole injection layer, an electron blocking layer, a hole blocking layer, an electron transport layer, and an electron injection layer, or a combination of at least two thereof.
15. An electronic device characterized in that it comprises a display panel as claimed in claim 13 or 14.
Priority Applications (2)
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| CN111635411A (en) * | 2020-06-30 | 2020-09-08 | 武汉天马微电子有限公司 | Organic compound, electroluminescent material and application thereof |
| CN111763223A (en) * | 2020-06-30 | 2020-10-13 | 武汉天马微电子有限公司 | Organic compound, thermal activation delayed fluorescent material and application thereof |
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| CN114380854B (en) * | 2022-01-27 | 2024-04-16 | 武汉天马微电子有限公司 | Organic compound, thermal activation delay fluorescent material and application thereof |
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| US20170141311A1 (en) * | 2014-07-03 | 2017-05-18 | Duk San Neolux Co., Ltd. | Compound for organic electronic element, organic electronic element using same, and electronic device comprising same |
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| CN110078755B (en) | 2019-05-30 | 2022-01-11 | 武汉天马微电子有限公司 | Compound, display panel and display device |
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| CN111763223B (en) * | 2020-06-30 | 2023-04-28 | 武汉天马微电子有限公司 | Organic compound, thermal activation delay fluorescent material and application thereof |
| CN111635411B (en) * | 2020-06-30 | 2023-10-10 | 武汉天马微电子有限公司 | Organic compound, electroluminescent material and application thereof |
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| US20200259088A1 (en) | 2020-08-13 |
| US11539004B2 (en) | 2022-12-27 |
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